Phthalocyanine dyestuffs



United States Patent 3,334,116 PHTHALOCYANINE DYESTUFFS Wilson J. Bryan, 'Jr., Charlotte, Thomas E. Lesslie, Mount Holly, and Gordon A. Geselbracht, Charlotte, N.C., assignors to Martin-Marietta Corporation, a corporation of Maryland No Drawing. Filed June 8, 1964, Ser. No. 373,576 6 Claims. (Cl. 260-3145) The present invention relates to p'hthalocyanine dyestuffs and to the method for making same.

The phthalocyanine dyestuifs of the present invention may be represented by the formula wherein Fe is the radical of a phthalocyanine; Y is a member selected from the group consisting of H (SO Na) (--SO K), and

R is a member selected from the group consisting of hydrogen, halogen, alkoxy and alkyl; Z is a member selected from the group consisting of --NH NH lower alkyl,

lower alkyl lower alkyl NH-aryl, -NHNH NH-NH-aryl, NHOH, NHNH-lower alkyl, and

lower alkyl NHN lower alkyl m is a number from 1-3; n is a number from 1-3; p is a number from 0-2; and the sum of m+n+p is a number from 2-4.

The dyestufls of the above formula may be synthesized Patented Aug. 1, 1967 'ice 'by a process comprising the steps of condensing a molecular proportion of with molecular proportions of a compound of the formula Z sw wherein W is a member selected from the group consisting of SO N-a, SO K, and

and condensing the resulting condensate with n molecular proportions of HZ, wherein Pc, R, Z, m, n, p, and m+n+p are as above defined, and x is the number of amino groups per molecule of R H o R 1 so -NH@ and they may be synthesized by condensing a molecular proportion of SO Cl r- 2 1m with m molecular proportions of and condensing the resulting condensate with n molecular proportions of HZ, wherein Pc, Z, R, m, n, and m+n+p are as above defined, and A is a member selected from the group consisting of Na and K. The Bunte salt form of the dyes may be isolated by evaporating to dryness the Bunte salt solutions resulting from the condensation step. In preparing the Na Bunte salt, the condensation will be conducted in the presence of a sodium base, and in preparing the K Bunte salt, the condensation will be conducted in the presence of a potassium base.

In the mercapto "form, the dyes of the present invention 'have the formula R J o sn m f z l SO3H]P and they may be synthesized by hydrolyzing the above Bunte salt form with acid.

In the disulfide form, the dyes of the present invention have the formula ,7 R SO -NH@ @NH-O s s-s m and they may be synthesized by condensing a molecular proportion of Pc -ESOaH] with molecular proportions of R R. we o s-s and condensing the resulting condensate with n molecular proportions of HZ, wherein Pc, R, Z, m, n, p, and m-l-n-l-p are as above defined and x is the number of amino groups per molecule of The dyestuffs of the present invention are particularly suitable for coloring a number of textile materials, such as cotton and regenerated cellulose, without limitation thereto.

The dyestuffs of the present invention have a number of advantages, some of which follow.

The dyestuffs are particularly characterized by their brilliance, light fastness, wash fastness, lack of off-tone fading, high tinctorial value, sulfide solubility, and ease of application to textile fibers by the reduction-oxidation method. The dyestuffs are further characterized by excellent properties of penetration into cotton and regenerated cellulose fibers. If desired, the dyes of the present invention may be reacted with formaldehyde to replace hydrogen atoms attached to nitrogen atoms with methylol groups, thereby providing dyes with the following valuable properties, e.g. fixability of the dye to textile fibers by means of the methylol group, and dyeability in combination with resins, such as formaldehyde condensation resins, wherein the dye and resin are co-condensed.

The following are specific and non-limiting examples of methods of embodying the present invention. All parts in these examples are by weight unless otherwise specified.

Example 1 The bright blue dyestuff of the formula wherein Fe is the radical of copper phthalocyanine, may be prepared as follows.

77.3 parts (0.10 mol) of copper phthalocyanine disulfonyl chloride are slurried with ice and water at 0 C. to 1,000 parts, and adjusted to pH 5.5-6.0 by adding 20% aqueous Na CO 25.0 parts (0.11 mol) of sodium S-4-aminophenylthiosulfate and 5 parts of pyridine catalyst are added thereto; the resulting mass is stirred for 1-2 hours at 0 C. while pH 7.0 is maintained by adding 42 parts 20% aqueous Na CO as needed, thereby permitting condensation.

parts 29% aqueous ammonia are added to the resulting condensate; the mass is warmed to room temperature and stirred 24 hours to effect a second condensation. At this stage the dyest-ulf exists as a solution of the Bunte salt, and if desired, this solution may be evaporated to dryness and isolated as wherein Fe is the radical of copper phthalocyanine.

(The corresponding potassium Bunte salt may be prepared by substituting an equimolar amount of potassium S-4-aminophenylthiosulfate for the sodium S-4-aminophenylthiosulfate, and KOH or K CO for the Na CO in the above).

The above mercapto (SH) form of the dyestulf may be prepared by hydrolyzing the above solution of the Bunte salt with an acid, such as by adding 850 parts 32% HCl and heating at reflux 6 hours.

The dytstuff is isolated by cooling the mass to 50 C., filtering, collecting the solids, washing the solids acid free with Warm Water, and optionally drying or preserving in the moist condition for subsequent use in preparation of a printing paste.

In the examples given in the following table the procedure is the same as that given in Example 1, and the examples in the table indicate that a molecular proportion of the particular phthalocyanine disulfonyl chloride in the second column is reacted with a molecular proportion of the thiosulfate in the third column, and the result condensed with a molecular proportion of the HZ compound in the fourth column to produce the dye shown by structural formula in the fifth column, in which formula Pc represents the radical of the phthalocyanine portion of the sulfonyl chloride shown in the second column.

Ex. Phthalocyanine disull'onyl Thiosuliate HZ Dye Color No. chloride I SH ;|-ESONH -o1 2 Cobalt phthalocyanine Potassium S-(-amino-2- Methylamlneun Pc Bh disulionyl chloride. chlorophenyl)thiosulfate. I" 1 LSOzNH-CHz] r SH zNH O I OCHa 3 Nickel phthalocyenine Sodium S-(2-amino-4- Dimethylamine... Pc Gr en,

disulfonyl chloride. methoxyphenyl(thio- L CH3 sulfate.

SO2N

CH3 T (llHa ISOrNH- SH 4 Phthalooyanine disulfonyl Sodium S-(4-amino-3- Aniline Pe B1 chloride. methylphenyDthio- L'- sulfate. SO -NH 0 1 p i[SOzNH- Q)srr] 5 Copper phthalocyanine Sodium S-4-aminopheny1- Hydrazlne Po Green,

disulfonyl chloride. thiosuli'ate.

SUg-NHNH2] L Example 6 (0.11 mol) of sodium S-(4-amino-3-bromophenyl)thio- The blue dyestuff of the formula sulfate are substituted for the sodium S-4-am1nophenylthiosulfate of Example 1, and except that the amount of ammonia is increased to 200 parts. v SH 40 In the examples given in the following table the pro- TE 0 cedure is the same as that given in Example 6, and the Pe examples in the table indicate that a molecular proportion of the particular phthalocyanine trisulfonyl chloride wherein P0 is the radical of phthalocyanine, may be prepared as follows.

This example is the same as Example 1 above, except that 81.0 parts (0.10 mol) of phthalocyanine trisulfonyl chloride are substituted for the copper phthalocyanine diin the second column is reacted with a molecular proportion of the thiosulfate in the third column, the result condensed with two molecular proportions of the HZ compound in the fourth column to produce the dye shown by structural formula in the fifth column, in which formula Pc represents the radical of the phthalocyanine porsulfonyl chloride of Example 1, except that 33.7 parts n f the Sulfonyl chloride in the SeCOnd C ll1mn.

Ex. Phthaloeyanine trisulfonyl Thiosulfate HZ Dye Color N0. chloride SH T-SOr-NH 9% 7 Nickel phthalocyanine Potassium S-(3arnino-5- Aniline Pc CH3-CH B1 e trisulfonyl chloride. ethoxyphenyl)thiosullate.

l E 3 ISOn-NH@CH 8 Cobalt phthalocyaaine Sodium S-(2-amino-5-ethyl- Diethylamlne Po Green,

trisulfonyl chloride. phenyDthiosulfate. I CHa-CHa SOz-N CHPCHa 2 -S0lNH- Q SH] 9 Copper phthalocyanine Sodium S-4-aminophenyl- Ethylamine 1 0 Do.

trisulfonyl chloride. thiosulfate. L l" S0zNHCHzCHa Ex. Phthaloeyanine trisulfonyl Thiosulfate HZ Dye Color No. chloride SII-I -SO NH 10 Phthalocyanine trisul- Sodium leg-f-aminophenyl- Phenylhydrazme 1|c D t e. fonylchloride io u a FSOrNH NH- :I L 1 -Es0,-NH O -sr1] 11 Copper phthalooyanine Sodium S-4-amlnophenyl- 4-nitropheny1- Po d ti 'osulfate. h drazme. I trisulfonylchlori e n y FSOPNH NH 6 N02] "T Example 12 phenyl)thiosu1fate are substituted for the sodium 8-4- The blue dyestuff of the formula aminophenylthiosulfate of Example 1, except that the OCH;

amount of ammonia is increased to 200 parts, and except that 5 parts of 4-picoline are substituted for the pyridine of Example 1.

In the examples given in the following table the procedure is the same as that given in Example 12, and the examples given in the table indicate that a molecule proportion phthalocyanine tetrasulfonyl chloride in the second column is reacted with a molecular proportion of the thiosulfate in the third column, and the result condensed with three molecular proportions of the HZ compound in the fourth column to produce the dye shown by structural formula in the fifth column, in which Formula Pc represents the radical of the phthalocyanine portion of the sulfonyl chloride shown in the second column.

Ex. Phthalocyanine tetra- Thlosuliate HZ Dye Color No. sultonyl chloride SH l- SO2NH 13 Cobalt phthalocyauine Sodium S-(3-amir1o- 5- Aniline Pc CH Green tetrasulfonyl chloride. methylphenyl)thiosuh'ate. LP

-S Oz-NH Q SH I sorNH- O 14 Copper phthalocyanine Potassium S-Z-aminophenyl Methylethyl- Pc tetrasulfonyl chloride. thiosulfate. amine. L CHr-CHa SOr-N L i-S0zNH- 0 SH 15 Phthalocyanine tetra- Sodium S-(tamino-Ii-fluoro- Methylamine Pc Do.

sulfonyl chloride. phenyl) thiosuliate. I

S Oz-NHCH3 L a SH -SOzNH- O 16..." Cobalt phthalocyanine Sodium S-(2-amino-4-ehloro- Methylhydrazine Po L (31 tetrasulfonyl chloride. phenyDthiosuliate.

[SOz-N11NHCH:]

Example 17 V The blue dyestuff of the formula 10 tion, whereupon the dye is in the form of a solution of the thiosulfuric acid salt.

If desired, the dyestufl may be isolated at this point as the thiosulfuric acid salt (4-SO Na) by evaporat- CH -CH I a a 5 111g to dryness, or it may be hydrolyzed and recovered in f) the mercapto (SH) form as follows.

L 170 parts 98% H 80 are added to the resulting condensate; the temperature of the mass is gradually raised etsorNHi] to reflux during a period of 3 hours, and reflux is maintained 12 hours.

FSOSJH The dyestufi is isolated by cooling the mass to 50 C., L filtering, collecting the solids, washing the solids acid free with warm water, and optionally drying or preserving wherein Pc i the radical f b lt phthalocyanine may in the moist condition for subsequent use in the preparabe produced as follows. 15 tion of a printing paste.

84.9 parts (0.10 mol) of cobalt phthalocyanine disul- In the examples given in the following table, the profonyl chloride monosulfonic acid are slurried with ice cedure is the same as that given in Example 17, and the and Water at 0 C. to 800 parts, and adjusted to pH 5.5- examples in the tables indicate that a molecular propor- 6.0 by adding aqueous Na CO 28.1 parts (0.11 tion of the particular phthalocyanine disulfonyl chloride mole) of sodium S-(4-amino-3-ethylphenyl)thiosulfate 20 monosulfonic acid in the secondcolumn is reacted with and 5 parts of 3-picoline catalyst are added thereto; the molecular proportion of the thiosulf'ate in the third colresulting mass is stirred at 0 C. l-2 hrs. While pH 7.0 urnn, and the result condensed with a molecular proporis maintained by adding 42 parts 20% aqueous Na CO tion of the HZ compound in the fourth column to proas needed, thereby permitting condensation. duce the dye shown in the fifth column, in which formula 180 parts 29% aqueous ammonia are added to the Pc represents the radical of the phthalocyanine portion resulting condensate; the mass is warmed to room temof the disulfonyl monosulfonic acid shown in the second perature and stirred 24 hours to effect a second condensacolumn.

Ex. Phthalocyanine rlisulfonyl Thiosolfate HZ Dye Color No. chloride monosulfonic acid 1 t ES0zNH 0 18 Copper phthalocyanine Sodium S-3-arn1nophen3l 2-ehloroamlme Pc SOT-NH 0 Bl disulfonyl chloride thiosulfate. monsulfonic acid. l

01 PESOSH] SOZNH 0 o1 /CH3 19 Phthalocyanine disulfonyl Potassium S-(2-amino'3- Dimethylamine-.- Pc- --SO:N Green.

chloride monosulfonic chlorophenyl)thiosulfate. acid. CH3

SOaI-I] OCHr-CH: -SO2NH 0 -sn 20 Nickel phthalocyanine Sodium S-(4-amino-3- Methylamine PCSO:NHCH5] Do.

disulfonyl chloride ethoxyphenyl)thiosuliate. I mouosulfonic acid. 7

soirr] SOzNH- 0 CH3 21 d0 Sodium S-(Z-amino-fi- 1,1-dimethyl- PCSO3NHN Do.

methylphenyl)thiosulfate. hydrazine.

SOaH] 1 1 Example 22 The green dyest-uff of the formula CH2 CH3 SO2NH CHa-CH; 2

wherein Pc is the radical of copper phthalocyanine, may 20 be produced as follows.

This example is the same as Example 17 above, except that 95.2 parts (0.10 mol) of copper phthalocyanine trisulfonyl chloride monosulfonic acid are substituted for the cobalt phthalocyanine disulfonyl chloride monosulfonic acid of Example 17; except that 25 parts (0.11 mol) of sodium S-4-aminophenylthiosulfate are substituted for the sodium S-(4-amino-3-ethylphenyl)thiosulfate of Example 17 and except that 51.1 parts of diethylamine are substituted for the ammonia of Example 17.

In the examples given in the following table, the procedure is the same as that given in Example 22, and the examples in the table indicate that a molecular proportion of the particular phthalocyanine trisulfonyl chloride monosulfonic acid in the second column is reacted with a molecular portion of the thiosulfate in the third column, and the result condensed with two molecular proportions of the HZ compound in the fourth column to produce the dye shown in the fifth column, in which formula Pc represents the radical of the phthalocyanine portion of the trisulfonyl chloride monosulfonic acid shown in the second column.

Ex. Phthnlocyaniue trisull'onyl Thiosulfate HZ Dye Color No. monosulfonic acid s0,-NH 0 Br 23 Phthalocyanine trisul- Potassium S-(fi-amino-Z- Methylamine. PC SOfl NHCH3] Green.

fonyl chloro monobromo phenyDthiosulfate. L z sulfonic acid.

SOzNH- 0 4) CH3 2L Nickel trisulfouly chloride Sodium S-(2-amino-4- Ammonia Pc SOrNHz] Blue.

monosulfonic acid. methoxyphenyl)thio- L sulfate.

SOPNH 0 SH 0 a 25 Cobalt trisulfonyl chloride Sodium S-(4-amino-3- B-phenetidiue- PeSO NH 0 Green. monosulfonic acid. methylphenyl)thiosulfate.

O CHz-CHs 1 --S 0 H] SOz-NH O SH 26. Copper trisulfonyl chlo- Sodium S-(4-arnino-3- 4-methylpheny1- Yc SOzNHNH 0 CH3 Do. ride monosulfonic acid methoxyphenyDthiohydrazine. L

sulfate.

1 3 Example 27 The blue dyestufi of the formula 14 Example 31 The turquoise dyestulf of the formula s0t NH- 0 SH rso -NH SH 1 L Y R I 0 a 0 so NH-OH PC-SO2NH2] a sour] 7 v wherein Pc is the radical of nickel phthalocyanine may be prepared as follows. wherein Pc is the radical of phthalocyanine, may be T eXamPie is the Same as Example 1 above; except produced as follows. that 86.7 parts (0.10 mol) of nickel phthalocyanine tri- This example i the same as Example 1 abo except sulfonyl chloride are substituted for the copper phthalothat 127.0 parts (0.10 mol) of phthalocyanine disulfonyl eyahihe disuifehyi ehiofide of E mp pt h chloride disulfonic acid are substituted for the copper the amount of sodium S-4-amihophehyithiosuifate is phthalocyanine disulfonyl chloride of Example 1, and creased to Parts mol), eXeePt that the amount except that 27.0 parts (0.11 mol) of sodium S-(4-amino- 20% aqueous z a added to maintain P is 2-fiuorophenyl)thiosulfate are substituted for the sodium 25 ihereased to 84 P and e p that P s f S-4-arninophenylthiosulfate of Exa 1 1, aqueous methylamine are substituted for the ammonia In the examples given in the following table the proceofExample I dure is the same as that given in Example 27; and the In the examples given in the following table the proceexamples in the table indicate that a molecular propordure is the same as given i Example d the examtion of the particular phthalocyanine disulfonyl chloride 30 P in h table. indicate h a molecule! Proportion of disulfonic acid in the second column is reacted with a the Particular phthalocyanine trisuitonyi Chloride in the molecular proportion of the thiosulfate in the thi d second column is reacted with two molecular proportions column, and the result condensed with a molecular pro- Of the thiosulfate in the third column, the result COH- portion of the HZ compound i th fo th ol to densed with one molecular proportion of the HZ comproduce the dye shown by structural formula in the fifth 35 pound in the fourth column to produce the dye shown column, in which formula Pc represents the radical of y s ru t ral f rmula in the fifth column, in which the phthalocyanine portion of the sulfonyl chloride shown formula Pc represents the radical of the phthalocyanine in the second column. portion of the sulfonyl chloride in the second column.

Ex. Phthalocyanine dlsulfonyl Thiosullate HZ Dye Color No. chloride disullonic acid SOT-NH O CHg-CHa 28 Cobalt phthalocyanine Sodium S-(2-amino-4-ethyl- Ethylamine PCS02NHCHgCH3] Green,

disulfonyl chloride diphenyDthiosulfate. sulfonic acid.

sour] 2 :so,-NH- 0 -SH] /0H;, -'29 ,Copper phthalocyanine Potassium S-4-am ino- Dimethylamine PCSOzNH Do, disulfouyl chloride diphenylthiosulfate.

sultonic acid. CH3

-'s0 H Y L a i I :s02r-i11 0 SH:|

30 Phthalocyanine disul- Sodium S-4-arninophenyl- Ethylhydrazine Pc-SO:-NHNHCHr-CH| Do.

7 tonyl chloride disulfonic thiosulfate. L acid."

-SO H Ex. Phthalocyauine Thiosulfate HZ Dye Color No. trisulfonyl chloride $11 Blue. sO2-NII Q Cobalt phthalocyanine Potassium S-(3-am1no-5- 32. trisulfonyl chloride. chlorophenyl)thiosull'ate. Ammonia Pc Cl 2 Ltsoum EH 0 CH3 ---s 0zN H l Q 33 Copper phthalocyanine Sodium S-(2-amino-6- Dirncthylamine... Pc Green,

trisulfonyl chloride. methoxyphenyDthiosul- F CH fate. SO1N\ CH3 SO2NH O ken 34 Phthalocyanine trisul- Sodium S-(4-amlno-2- Aniline Pc l CH 1 Do;

tonyl chloride. methylphenyl)thiosulfate.

'[SOz-NH O SH ,l-ESOz-NH 0 13:

2 35 Cobalt phthalocyanine SodiuJn'S-(ti-aminoZ-bromo- LI-diethylhydra- Pc Do.

trisulfonyl chloride. phenybthiosulfate. zine. l GHQ-CH3 L--S02NHN OH:CH3

Example 36 The green dyestuff of the formula I' 'SO2N HICHK 1 wherein Fe is the radical of cobalt phthalocyanine, is prepared as follows.

This example is the same as Example 17 above, except that 96.6 parts (0.10 mol) of cobalt phthalocyanine tetrasulfonyl chloride are substituted for the cobalt phthalocyanine disulfonyl chloride monosulfonic acid of Example 17, except that 70.9 parts (0.22 mol) potassium S-(4- amino 2 bromophenyl)thiosulfate are substituted for the sodium S-(4-amino-3-ethylphenyl)thiosulfate of Example 17, except that the amount of 20% aqueous Na CO added to maintain pH 7.0 is increased to 84 parts, and except that 35.4 parts of methylethylamine are substituted for the ammonia of Example 17.

In the examples given in the following table, the procedure is the same as that given in Example 36, and the examples in the table indicate that a molecular proportion of the particular phthalocyanine tetra sulfonyl chloride in the second column is reacted with two molecular proportions of the thiosulfate in the third column,' and the result condensed with two molecular proportions of the HZ compound in the fourth column to produce the dye shown in the fifth column, in which formula Pc represents the radical of the phthalocyanine portion of the tetrasulfonyl chloride shown in the second column.

Ex. Phthalocyanine Thiosulfate HZ Dye Color No. tetrasulfonyl chloride I" SH S O :NH I

O C Hz-C H: i L 1 Blue. 37 Copper phthacyaniue Sodium S-(-amino-2 Ammonia Pc tetrasulfonyl chloride. ethoxyphenyDthiosulfate. F

S O 1-NH: L SH -SOi---NH CH; l a Green. 38"-.- Phthalocyaniue tetra- Potassium S-(2-amlno-5- Methylamine Pc sulfonyl chloride. methylphenyl)thiosulfate.

S OzNH-C H;

1 1SOa-NH O -sn] i 39 Nickel phthalocyanine Sodium S-4-aminophenyl- Aniline Pc D0.

tetrasulfonyl chloride. thiosulfate. L

so,Nrr Q x Y-ESOz-NH O -sn] a 40"--- Nickel phthalocyanine Potassium S-4-amino- 3-methylphenyl- Pe Do.

tetrasulfonyl chloride: phenylthiosulfate. hydrazine. l I" G SOs-NH-NH (JJH: 2

Example 41 15% aqueous KOH as needed, thereby permitting con;

The green dyestufi of the formula OCHa l -Mm a as densation.

46.6 parts of aniline are added to the resulting condensate; the mass is stirred 3 hours at 0 C. and 20 hours at room temperature while 15% KOH is added to maintain pH 7, thereby effecting a second condensation, whereupon the dye is in the form of a solution of the thiosulfuric acid salt.

If desired, the dyestufi may be isolated at this point as the thiosulfuric acid salt (S--SO K) by evaporating to dryness, or it may be hydrolyzed and recovered in the mercapto (-SH) form as follows.

700 parts of 32% HCl are added to the resulting condensate and the mass heated at reflux 6 hours to effect hydrolysis to the mercapto form.

The dyestuflf is isolated by cooling the mass to 50 C., filtering, collecting the solids, Washing the solids acid free with warm water, and optionally drying or preserving in the moist condition for subsequent use in preparation of a printing paste.

1n the examples given in the following table the procedure is the same as that given in Example 41, and the examples in the table indicate that a molecular proportion of the particular phthalocyanine trisulfonyl chloride monosulfuric acid in the second column is reacted with two molecular proportions of the thiosulfate in the third column, and the result condensed with a molecular proportion of the HZ compound in the fourth column to produce the dye shown by structural formula in the fifth column, in which formula Pc represents the radical of the phthalocyanine portion of the sulfonyl chloride shown in the second column.

Ex. Phthalocyaniue trisulfonyl Thiosulfate HZ Dye Color N0. chloride monosuli'onic acid I SH SOr-NH- 0 Green. 42"--- Phthalocyanine trlsul- Potassium S-(3-amino 5- Methylamlne PcSO1-NHCHs fonyl chloride monomethylphenybthioaulfate. L sulfonic acid.

ES 03H] I SH -S0:NH

43- Nickel phthalocyaniue Sodium S-2-aminophenyl- Ammonia Pe S 02-NH1] Blue.

trisulionyl chloride thiosulfatc. L monosulfouic acid.

I" F -S0 NH O H; Green. 44- Cobalt phthalocyanine Sodium S-(4-amino-2-fluoro- Dimcthylamlue Pc S Oz-N trisulfonyl chloride phenyDtlriosulfatc. L mouosulfonic acid. 0 H3 CHz-C H; S 0,NH

Do. 4.5L Copper phthalocyaniue Sodium S-(4-amino-2-ethyl- Hydrazlne P0-SO2-NHNH7 trisulionyl chloride phenyDthiosulfate. L monosulionic acid.

Example 46 90.9 parts 0.10 mol) of phthalocyanine tetrasulfonyl The turquoise dyestufi of the formula wherein Pc is the radical of phthalocyanine may be prepared as follows.

This example is the same as Example 1, except that 75 chloride are substituted for the copper phthalocyanine disulfonyl chloride of Example 1, except that 78.6 parts (0.33 mol) of sodium S-(4-amino-2-methylphenyl)thiosulfate are substituted for the sodium S-4-aminophenylthiosulfate of Example 1, and except that the amount of 20% aqueous Na CO added to maintain pH 7.0 is increased to 126 parts.

In the examples given in the following table the procedure is the same as that given in Example 46, and the examples in the table indicate that a molecular proportion of the particular phthalocyanine tetrasulfonyl chlo ride in the second column is reacted with three molecular proportions of the thiosu lfate in the third column, the result condensed with a molecular proportion of the HZ compound in the fourth column to produce the dye shown by structural formula in the fifth column, in which formula Pc represents the radical of the phthalocyanine portion of the sulfonyl chloride in the second column.

Ex. Phthalocyanine Thiosulfate HZ Dye Color No. tetrasulfonyl chloride F SH I-SO2NH 6 47 Nickel phthalocyanine Sodium S-B-aminophenyl- Methylamine Po 3 Green.

tetrasulfonyl chloride. thiosulfate. I

S O g-NH-C H3] S SO2NH F O 48.-. Cobalt phthalocyanine Sodium S-(2-amino-5- Aniline Pc a Do.

tetrasulfonyl chloride. ehlorophenybthiosultate.

soiNH L F CH3 SO2-NH F 0 SH a 49 Copper phthalocyanine Potassium S-(4-amino-2- Dimethylamine-. Pc Do.

tetrasulfonyl chloride. %ntethoxyphenyl)thiosul- /CH3 S O2-NH 3 {SO:NH 0 SH 50 Phthalocyanine tetra- Sodium S-4-aminophenyl- 1-methyl-1-ethy1-. Pc 3 Do.

sulfonyl chloride. thiosulfate. hydrazine. /CH

SOz-NH-N\ :I CHr-CH;

Example 51 86.7 parts (0.1 mol) cobalt phthalocyanine trisulfonyl The blue dyestufi of the formula wherein Fe is the radical of copper phthalocyanine, may be prepared as follows.

77.3 parts (0.1 mol) copper phthalocyanine' disulfonyl chloride are slurried with 700 parts acetone; 13.6 parts (0.05 mol) 4,4-diaminodiphenyldisulfide and 100 parts pyridine are added thereto; the mass is stirred at room temperature 2 hours, thereby permitting condensation.

200 parts 29% aqueous ammonia are added to the resulting condensate, and stirred 24 hours at room temperature to elfect a second condensation.

Isolation of the dye is effected as follows. The pH of the condensate is adjusted to 3.0 or less by addition of HCl. The condensate is filtered, the resulting solids washed with 5% aqueous HCl to remove excess diaminodiphenyldisulfide, and then washed free of HCl with water. The resulting dye solids may be dried, or may be preserved in the moist condition for subsequent preparation of a printing paste.

Example 52 The green dyestufi of the formula LS0 NH (EH12 wherein Fe is the radical of cobalt phthalocyanine, may be prepared as follows.

chloride are slurried with ice and water at 0 C. to 1,000 parts, 17.4 parts (0.05 mol) 3,3'-diamino-5,5'-dichlorodiphenyldisulfide and 10 parts pyridine catalyst are added thereto, and the pH of the resulting mass is adjusted to pH 3.5 with 32% aqueous HCl; while maintaining pH 3.5 by addition of 10% aqueous Na CO as needed, the mass is stirred at 03 C. for 3 hours, gradually warmed to room temperature with stirring during 5 hours, and stirred at room temperature 14 hours, thereby permitting condensation.

62.1 parts 30% aqueous methylamine are added to the resulting condensate; the mass is stirred at room temperature 24 hours to eifect a second condensation.

The dyestutf is isolated and recovered as in Example 51 above.

Example 53 The green dyestulf of the formula dimethylamine are substituted for the methylamine of Example 52.

Example 54 The green dyestulf of the formula wherein Pc is the radical of phthalocyanine, may be prepared as follows.

This example is the same as Example 51 above, except that 79.2 parts (0.1 mol) phthalocyanine disulfonyl chloride monosulfonic acid are substituted for the copper phthalocyanine disulfonyl chloride of Example 51. 22.3 parts (0.05 mol) 4,4-diamino-2,2-dibromodiphenyldisulfide are substituted for the 4,4-diaminodiphenydisulfide of Example 51, and except that 46.6 parts aniline are substituted for the ammonia of Example 51.

wherein P0 is the radical of copper phthalocyanine may be prepared as follows.

This example is the same as Example 52 above, except that 95.2 parts (0.1 mol) copper phthalocyanine trisulfonyl chloride monosulfonic acid are substituted for the cobalt phthalocyanine trisulfonyl chloride of Example 52, except that 16.9 parts (0.05 mol) 3,3-diamino-4,4-dimethoxydiphenyldisulfide are substituted for the 3,3'-diamino-5,5-dichlorodiphenyldisulfide of Example 52, and 61 parts 85% hydrazine hydrate are substituted for the methylamine of Example 52.

Example 56 The green dyestutf of the formula wherein Fe is the radical of cobalt phthalocyanine, may be prepared as follows.

132.7 parts (0.1 mol) cobalt phthalocyanine disulfonyl chloride disulfonic acid are slurried with ice and water at 0 C. to 1,000 parts, 15.2 parts (0.05 mol) 2,2-diamino- 6,6-dimethyldiphenyldisulfide and parts 4-picoline catalyst are added thereto, and the pH of the resulting mass is adjusted to pH 3.5 with 32% aqueous HCl; while maintaining pH 3.5 by addition of 7.5% aqueous NaOH as needed, the mass is stirred at 03 C. for 3 hours, gradually warmed to room temperature with stirring during 5 hours, and stirred at room temperature 14 hours, thereby permitting condensation.

27.8 parts phenylhydrazine hydrochloride are added to the resulting condensate with enough ice to cool the mass to 0 C.; the pH of the mass is adjusted to pH 7.0 with 7.5% aqueous NaOH and there maintained while the mass is stirred at 0-3 C. for 3 hours, gradually warmed to room temperature with stirring during 5 hours, and stirred at room temperature 14'hours, thereby effecting a second condensation.

The resulting dyestuff is isolated and collected as in Example 51.

Example 57 OCH2-CH3 LTSO2-NHNHOH [CHaNHNH02S3- wherein P0 is the radical of nickel phthalocyanine may be prepared as follows.

This example is the same as Example 56 above, except that 86.7 parts (0.1 mol) nickel phthalocyanine trisulfonyl chloride are substituted for the cobalt phthalocyanine disulfonyl chloride disulfonic acid of Example 56, except 36.9 parts (0.11 mol) 4,4-diamino-3,3-diethoxydiphenyldisulfide are substituted for the 2,2 diamino 6,6 dimethyldiphenyldisulfide of Example 56, and except that 21.7 parts methylhydrazine sulfate are substituted for the phenylhydrazine hydrochloride of Example 56.

Example 58 The green dyestulf of the formula C'Hr-CHa (3 2-0112 -so NH O s-s NH-O st L if Tl Example 59 The blue dyestufr of the formula l bl wherein Pc represents the radical of copper phthalocyanine may be prepared as follows.

95.2 parts (0.1 mol) copper phthalocyanine trisulfonyl chloride monosulfonic acid are slurried with ice and water to 1,000 parts, 27.3 parts (0.11 mol) 2,2 diaminodiphenyldisulfide and 10 parts of 3 picoline catalyst are added thereto, and the pH of the resulting mass is adjusted to 3.5 with 32% aqueous HCl; while maintaining pH 3.5 by the addition of 10% aqueous Na CO the mass is stirred at -3 C. for 3 hours, gradually warmed to room temperature with stirring during hours, stirred at room temperature 14 hours, thereby permitting condensation.

492 parts 3-anisidine are added to the resulting condensate; the mass is stirred at room temperature 24 hours to eifect a second condensation.

The dyestutf is isolated and recovered as in Example 51 above.

Example 60 The blue dyestutf of the formula SO. NH sin-ma 8 5 1 wherein Pc represents the radical of copper phthalocyanine may be prepared as follows.

This example is the same as Example 59 above except 97.0 parts (0.1 mol) of copper phthalocyanine tetrasulfonyl chloride are substituted for the copper phthalocy anine trisulfonyl chloride monosulfuric acid of Example 59, except that 409 parts (0.16 mol) of 4,4 diaminodiphenyldisulfide are substituted for the 2,2 diaminodiphenyldisulfide of Example 59, except that 5 parts 3,4- picolines catalyst are substituted for the 3-picoline of Example 59, and except that 51.0 parts 2-chloroaniline are substituted for the 3-anisidine of Example 59.

Pc-SOrNHz] L -ESonaJ wherein Pc is the radical of copper phthalocyanine, may be prepared as follows.

175 parts 99.8% copper phthalocyanine are added evenly during one hour to 1130 parts chlorosulfonic acid being stirred at 20-40 C.; the temperature is raised during a period of one hour to 135 C. and then maintained at 135-140 C. for 3 additional hours, cooled to 85 C. during 30 minutes; held at 8085 C. for 1 hr. while 147 parts 98% thionyl chloride are added thereto; stirred 3 additional hours at 80"85 C.; and cooled to room temperature. The mass is drowned in ice and water at 0 C., causing precipitation; the precipitate is filtered at 0 C., and washed acid free with water at 0 C.

The precipitate is slurried with ice and water at 0 C. to 2,000 parts; adjusted to pH 5.5-6.0 by adding 20% aqueous Na CO 86.0 parts sodium S-4-aminophenylthiosulfate and 20 parts pyridine, catalyst are added thereto. The resulting mass is stirred 95 minutes at 0 C. while pH 7.0 is maintained by adding 240 parts 20% aqueous Na CO 540 parts 29% aqueous ammonia are added while the temperature is maintained at 0 C. The mass is stirred 3 hours at 0 C., warmed evenly during 5 hours to room temperature, and stirred 16 hours at room temperature, whereupon the dye is in the form of a solution of its thiosulfuric acid salt.

If desired, the dyestulf may be isolated at this point as its thio surfuric acid salt (S-SO Na) by evaporating to dryness, or it may be hydrolyzed and recovered in its mercapto (AH) form as follows.

410 parts 98% H 50 are added to the thiosulfuric acid salt solution, and the mass is heated evenly to reflux during 5 hours, and reflux is maintained for 12 hours. The dyestuif is isolated and recovered as in Example 1.

Example 62 The bright green phthalocyanine dyestuif of the formula SOaH] 0.5

Example 63 The blue dyestuif of the formula wherein Pc is the radical of copper phthalocyanine may be prepared as follows.

This example is the same as Example 61 above, except that the amount of Na CO is reduced from 240 parts to 200 during the condensation with sodium S-4-aminophenylthiosulfate, except that 53.9 parts 98.7% hydroxylamine hydrochloride are substituted for the aqueous ammonia, and except that enough 20% aqueous Na CO is added to maintain pH 7.0 during condensation with the hydroxylamine.

The dyestufi may be isolated as the thiosulfuric acid salt (-SSO Na), shown above, or in the mercapto (SH) form in the manner described in Example 61.

Example 64 The blue dyestulf of the formula may be prepared as follows.

This example is the same as Example 51 above, except that 200 parts of 7.11% aqueous hydroxylamine hydrochloride, adjusted to pH 7.0 with alkali, are substituted for the aqueous ammonia of Example 51.

All of the dyes of the present invention may be applied to cotton fabric by padding onto the fabric a composition comprising 20 parts dye, 945 parts water, and 35 parts 60% sodium sulfide, squeezing the fabric to 70% wet pick-up based on fabric weight, drying the fabric, steaming the fabric, passing the fabric into a chemical oxidizing bath comprising 985 parts water, 7.5 parts sodium dichromate, and 7.5 parts glacial acetic acid, scouring and drying the fabric.

The thiosulfuric acid salt forms of the dyes of the present invention may be applied to cotton fabric by padding onto the fabric a composition comprising 25 parts thiosulfuric acid salt form of the dye, 825 parts water,

50 parts thiourea and 100 parts urea, drying the fabric, passing the fabric for 90 seconds into a curing oven heated to 410 F., and optionally scouring and drying the fabric.

What is claimed is:

1. A phthalocyanine dyestuff of the formula R SO2-NH-@\ s m Y SO H 31 wherein Pc is the radical of a phthalocyanine selected from the group consisting of copper phthalocyanine, cobalt phthalocyanine, nickel phthalocyanine and phthalocyanine; Y is a member selected from the group consisting of H (SO Na) (SO K) and R is a member selected from the group consisting of hydrogen, halogen, alkoxy having one or two C atoms, and alkyl having one or two C atoms; Z is a member selected from the group consisting of NH NH-lower alkyl,

from 24.

2. A dyestulf of the formula SOg-NH@ CuPc ESO -Z] n s l P wherein CuPc is the radical of copper phthalocyanine; R is a member selected from the group consisting of hydrogen, halogen, alkoxy having one or two C atoms, and alkyl having one or two C atoms; Z is a member selected from the group consisting of NH NH-lower alkyl,

lower alkyl lower alkyl lower alkyl NHN lower alkyl m is a number from 13; 11 is a number from l-3; p is a number from 0-2; and the sum of m1 +n+p is a number from 2-4.

3. A dyestuif of the formula so -NH@ SSO Na m wherein CuPc, R, Z, m, n, p, and the sum of m+n+p are as defined in claim 2.

4. A dyestuff of the formula R R SO -NH-@ @mH-o s s-s wherein CuPc, R, Z, m, n, p, and the sum of m+n+p are as defined in claim 2.

5. The dyestulf of the formula wherein CuPc is the radical of copper phthalocyanine.

6. The dyestulf of the formula F 1 so H a wherein CuPc is the radical of copper phthalocyanine.

References Cited UNITED STATES PATENTS 3,226,395 12/1965 Schimmelschmidt et al.

260314.5 3,236,860 2/1966 Schultheis et al. 260-3145 FOREIGN PATENTS 749,349 5/ 1956 Great Britain.

OTHER REFERENCES Belgian Chemical Abstracts, vol. 57 (1962), p. 16809e.

WALTER A. MODANCE, Primary Examiner.

JAMES A. PATTEN, Assistant Examiner.

UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No 3 ,334 ,ll6 August 1 1967 Wilson J. Bryan, Jr., et al.

It is hereby certified that error appears in the above numbered patent requiring correction and that the said Letters Patent should read as corrected below.

Column 4, line 59, for "dytstuff" read dyestuff columns 5 and 6, Example 2, in the structural formula, for

SH @Cl read Example 3, second column, for "methoxyphenyl(thio-" read methoxyphenyl)thio same Example 3, in the structural formula, for 5 H read OCH 2 OCH 8, in the structural formula for column 14, Example SH iH -CH CH -CH Columns 19 and 20 Example 44 in the structural formula, for "-SH read Sfl Example 45 in the structural formula, for CH CH Z S read columns 21 and 22 Example 48 in the structural formula for 5 SH @Cl read same columns, Example 50, in the structural formula for CH CH read CH CH column 25 line 75 for "thio surfuric" read thiosulfuric Signed and sealed this 9th day of July 1968.

(SEAL) Attest:

EDWARD M.PLETCHER,JR. EDWARD J. BRENNER Attesting Officer Commissioner of Patents 

1. A PHTHALOCYANINE DYESTUFF OF THE FORMULA 